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Catalytic formation of carbon monoxide (CO) and hydrogen (H2) from biomass

a carbon monoxide and biomass technology, applied in the preparation of carboxylic compounds, combustible gas catalytic treatment, physical/chemical process catalysts, etc., can solve the problems of reducing the yield of reaction, and simple acids to hydrolyze cellulose selectively. , to achieve the effect of increasing the yield of reaction

Inactive Publication Date: 2018-01-23
YEDA RES & DEV CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The present invention is based on the unexpected discovery that certain catalysts can efficiently convert various forms of biomass (including lignin, cellulose, and hemicellulose polysaccharides) and carbohydrates into a mixture of carbon monoxide (CO) and hydrogen (H2) using mild conditions. This CO and H2 can then be combined in any desired ratio to create synthesis gas (Syngas), which can be further converted into hydrocarbons or other products. Additionally, this invention describes an improved process for preparing formic acid from carbohydrates using a polyoxometalate catalyst and methanol or an alcohol / water mixture as the reaction solvent. The use of an alcohol solvent significantly increases the yield of the reaction.

Problems solved by technology

Solar energy and solar fuels have been touted as the ultimate, indefatigable sources of energy, but the storage of sunlight and its use in a practical way remains a major challenge of modern times.
(1,2) The transformation of cellulose to D-glucose, its sole component, and then to ethanol to be used as a biofuel by fermentation is perhaps the most developed technology, however the failure of simple acids to hydrolyze cellulose selectively (3) remains a problem that requires the use of more expensive cellusomes.
(4) The hydrolysis / fermentation approach also has the disadvantage that hemicellulose and its major hydrolysis product, D-xylose, still cannot be used to form ethanol.
(12) Despite the aforementioned advances, reaction selectivity is typically low and process schemes are quite complicated.

Method used

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  • Catalytic formation of carbon monoxide (CO) and hydrogen (H<sub>2</sub>) from biomass
  • Catalytic formation of carbon monoxide (CO) and hydrogen (H<sub>2</sub>) from biomass
  • Catalytic formation of carbon monoxide (CO) and hydrogen (H<sub>2</sub>) from biomass

Examples

Experimental program
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Effect test

example 1

Conversion of Glucose Under Aerobic Conditions

[0077]Based on mechanistic analysis of on electron transfer-oxygen transfer reactions catalyzed by H5PVV2Mo10O40 in general (22,23) and alcohols and vicinal alcohols in particular (15), it is contemplated that oxidation of D-glucose could yield 5 equivalents of HCOOH, 1 equivalent of HCHO and 6 equivalents of reduced polyoxometalate, H7PVIV2Mo10O40 according to a series of reactions presented in Scheme 2.

[0078]

[0079]Without wishing to be bound by any particular theory or mechanism of action, it is surmised to ideally proceed via an oxygen atom insertion from the polyoxometalate accompanied by carbon-carbon bond cleavage to yield formic acid (HCOOH) from the C-1 to C-5 carbon atoms and formaldehyde (HCHO) from the C-6 carbon atom. The deoxygenated and reduced polyoxometalate, H5PVIV2Mo10O39 reacts with H2O to yield H7PVIV2Mo10O40. If the reaction is carried out in the presence of O2, its reaction with H7PVIv2Mo10O40 will yield H5PVIV2Mo10...

example 2

Conversion of Carbohydrates Under Aerobic Conditions

[0083]The conversion of other carbohydrates was carried out by 100 mg reacting and 80 mg H5PV2Mo10O40 in 3 mL (1:1) methanol / water under 2 bar O2 at 110° C. for 18 h. The amount of products is given as per carbon atoms of substrate that reacted are given in Table 1.

[0084]

TABLE 1Aerobic oxidation of a variety of saccharides and polysaccharides.Conversion,HCOORH2C(OR)2Substratemol %R = H, CH3R = H, CH3CO2COD-glucose>994.700.920.38ndgluconic>994.000.591.090.22acidD-galactose>994.780.860.36ndD-mannose>994.660.910.43ndsorbitol[a]>993.891.550.390.17fructose>993.941.630.43ndxylan>993.840.780.38ndcellulose[b]~401.570.560.34ndnd—not detected.[a]30 h.[b]120° C., 30 h.

example 3

Conversion of Carbohydrates to CO in Concentrated H2SO4

[0085]According to Scheme 4, cellulose or hemicellulose can be transformed to CO and a reduced polyoxometalate. The cellulose used was microcrystalline powder from natural wood pulp and the hemicellulose was xylan from beech wood. Both were used without any pre-treatment. The reactions were carried out by mixing 100 mg polysaccharide and 7.80 g H5PV2Mo10O40 in 8 mL concentrated H2SO4 at 70° C. for 5 h under an N2 atmosphere. As the polyoxometalate is solvated by 36 water molecules, the concentration of H2SO4 during the reaction is ˜80%. There was complete conversion for both cellulose and hemicellulose and analysis of the gas phase by gas chromatography with a thermal conductivity detector (GC-TCD) showed the formation of only CO and CO2 in a ratio that was on the average 65±3:35±3 over five experiments. In addition, quantitative analysis using the GC-TCD with N2 as the internal standard showed quantitative formation, that is, ...

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Abstract

The present invention relates to methods of preparing carbon monoxide (CO) and hydrogen (H2) by reacting biomass, a biomass component (e.g., lignin, ligno-cellulose, cellulose, hemiceullose or combination thereof) or a carbohydrate from any source with a polyoxometalate catalyst such as H5PV2Mo10O40, or solvates thereof, in the presence of a concentrated acid, under conditions sufficient to yield carbon monoxide (CO); followed by electrochemical release of hydrogen (H2). The carbon monoxide (CO) and hydrogen (H2) may be combined in any desired proportion to yield synthesis gas (Syngas). The present invention further relates to methods for preparing H2, CO and formic acid / formaldehyde from biomass, a biomass component and / or from carbohydrates.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS[0001]This application is a National Phase Application of PCT International Application No. PCT / IL2014 / 050933, International Filing Date 28 Oct., 2014, claiming priority from United States Provisional Ser. No. 61 / 896,715 Patent Application, which is hereby incorporated by reference.FIELD OF THE INVENTION[0002]The present invention relates to methods of preparing carbon monoxide (CO) and hydrogen (H2) by reacting biomass, a biomass component (e.g., lignin, ligno-cellulose, cellulose, hemiceullose or combination thereof) or a carbohydrate from any source with a polyoxometalate catalyst such as H5PV2Mo10O40, or solvates thereof, in the presence of a concentrated acid, to yield carbon monoxide (CO); followed by electrochemical release of hydrogen (H2). The carbon monoxide (CO) and hydrogen (H2) may be combined in any desired proportion to yield synthesis gas (Syngas). The present invention further relates to methods for preparing H2, CO and formic ...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): C01B3/16C10G3/00C10G1/06C10K3/04C25B1/00C10K3/06C07C51/235C01B3/02B01J27/199C25B1/02C01B32/40
CPCC01B3/16B01J27/199C01B3/02C07C51/235C10G1/065C10G3/44C10K3/06C25B1/00C25B1/02C10K3/04Y02P30/20C01B2203/0283C01B2203/1041Y02E60/366C07C51/23C07C53/02Y02E60/36
Inventor NEUMANN, RONNYSARMA, BIDYUT-BIKASH
Owner YEDA RES & DEV CO LTD